Halogenated foots oil



vtained.

Patented Apr. 26, 1949 HALOGENATED roo'rs OIL Bert H. Lincoln, Ponca City, Okla., and Gordon D. Byrkit, Niagara Falls, N. Y., assignors, by mesne assignments, to The Lubrizol Development Corporation, a corporation of Delaware No Drawing. Application November 6, 1944,

Serial No. 562,266

10 Claims. (Cl. 252-488) This invention relates, as indicated, to halogenated foots oil and its method of preparation.

This application is a continuation in part of our copending application Serial No. 420,734, filed November 2'7, 1941 (now abandoned), in turn a continuation in part of our application Serial No. 299,186, filed October 12, 1939, now Patent No. 2,264,319. It is the principal object of our invention to provide a new composition of matter and method of producing the same, which, while having a wide variety of uses as hereinafter more fully explained, is particularly suitable for use as a component of compounded lubricating compositions particularly of the class having extreme pressure characteristics.

Another object of our invention is to provide an addition agent to impart anti-oxidant characteristic in a lubricant,

A further object of this invention is to provide an addition agent for a lubricant to serve as an inhibitor of corrosion.

Other objects of our invention will appear as the description proceeds.

Our invention, then, consists of the means hereinafter fully described and particularly pointed out in the claims, the following description setting forth in detail certain means embodying the invention, such disclosed means constituting, however, but some of the various ways in which the principle of the invention may be used.

Halogenated foots oil is as a rule stable to heat, light, and long standing and is of a sufliciently light color that when blended'with a lubricating oil it is unobjectionable to the retailer. Furthermore, when foots oil is halogenated, a homogeneous product is produced which does not require further treatment before it is ready for use as a halogen compound out other important properties are contributed by treatment with a sulfur hearing reagent. This is of particular advantage inasmuch as minor amounts, if left unhalogenated, would tend to elevate the pour point of the finished lubricant and, on the other hand, if a portion of the addition agent were too highly halo-.

genated, it might tend to become unstable. When foots oil is employed a uniform product is ob- In view of the difliculties encountered with certain other fractions of hydrocarbon oils these properties of foots oil were entirely unexpected and led to further experimentation to 1 determine whether its other properties were such as to render it a desirable extreme pressure addition agent.

Foots oil is unlike any other petroleum refinery product. It has properties that prevent its inclusion in a category with lubricating oil (neutral oil) fractions, Likewise, it may not be included with the waxes. Since it has chemical and physical properties different from lubricating oil and the waxes, it has been recognized as a petroleum fraction unlike all others. In practical refinery operations, it is removed with the wax from the raw wax distillate fraction for the production'of a satisfactory lubricating oil, the separation usually being accomplished by pressing. The foots oil is subsequently removed from the wax for the production of a, commercially salable wax. The term foots oil as used in this patent shall include the hydrocarbon fraction that is removed from petroleum in manufacturing petroleum wax and high grade lubricating stocks, said fraction having physical and chemical properties different from wax and neutral oil. The wax-foots oil separation is usually accomplished by sweating. Further proof of the fact thatfoots oil is unlike lubricating oil and unlike wax is obvious from the universal practice of using foots oil for the production of gasoline by thermal or catalytic cracking.

The foots oil employed in thisinvention may be refined or may be satisfactorily used as derived from petroleum processing. The refining may be accomplished by simple filtering, solvent extracting, clay contacting, clay percolation, sulfuric acid treatment, or any combination of these and other common refining processes. Very small amounts of sulfuricacid have been found sumcient for effective treatment of foots oil; forexample, fourtoten pounds of 98 Baum acid per barrel of foots oil followed by clay contacting for neutralization gives a very satisfactory product.

The raw or refined foots oil may be chlorinated by the usualmethods, and amounts of chlorine over a wide range may be used up to 60% and more. In the lower ranges, of from 10 to 25 per cent chlorine, a large proportion of the chlorine may be in relatively active form. In higher ranges, for example of 30 to 40 per cent of chlorine, a large percentage of the chlorine is in relatively stable form. When the desired amount as uncomblned chlorine or hydrogen chloride is.

removed. I

It has been found that the average molecular weight of foots oil is approximately 300. A monochlorinated foots oil has an average molecular weight of approximately 335. A 10.4 per cent chlorine content indicates a monochloro foots oil. A dichloro foots oil has a chlorine content of 18.9 per cent, and an octochloro foots oil has a chlorine content of 48.2 per cent. It is readily seen fromthis that the polyhalogenated foots oil will provide a desirable material for making the reaction products later described. In making the reaction product of this invention one or more halogens will be removed.

Commercial batches of chlorinated foots oil have been prepared by heating the unchlorinated foots oil to a temperature of from about 115 to 125 C. and chlorine gas passed through the chlorinated foots oil for periods varying from to 40 hours, depending upon the size of the batch and the degree of chlorination desired. The higher chlorinated material requires longer chlorination than the product containing a lesser amount of chlorine. The heat of reaction during the early stages of chlorination is suflicient to maintain the batch at an elevated temperature. Near the end of the chlorination period, however, it is usually necessary to supply additional heat to maintain such temperature. The chlorination has been most successfully performed in enamel lined vessels, that is, without the presence of a catalyst such as iron.

In the above description of the method of halogenating foots oil, chlorine is referred to. It is, however, within the scope of this invention to use any of the halogens, the method of preparation being substantially the same and well known to those skilled in the art, but chlorine is referred to as it is the cheapest and most available of .the halogens.

The halogenated foots oil may be further improved for certain uses by treatments which will remove the least stable part of the halogen, for example, by treatment with alkalies, aluminum chloride, inorganic sulphides, metallic xanthates,

Analyses of chlorinated foots oil The wet air stability test given in the foregoing table of analyses was determined by placing a anacea sample of the chlorinated foots oil in a 250 mm. flask and immersing the flask in an oil bath to maintain the temperature thereof at about 300 1". Air saturated with moisture at room temperature is blown through the sample and the HCl liberated was absorbed in a normal volume of standardized caustic and the amount of HCl liberated determined by titrating the caustic.

The "saponiflcation number corrected for chloride in the foregoing table was determined by the standard A. S. T. M. method D-94-41T. The method is carried out in accordance with this A. S. T. M. number and then the solution is made just sold with nitric acid and the chloride determined by titrating with tenth normal silver nitrate and the equivalent number of cc. of silver nitrate is subtracted from the titration to correct for chloride.

There follows one theory which may serve to explain the reason for the unexpected advantages of halogenated foots oil over other halogenated materials which have been proposed for the purpose. It is to be understood that this invention is not to be considered as limited in any way by such explanation.

The process of obtaining foots oil may be con- I sidered a double fractionation in that the chilling and pressing operations separate lubricating hydrocarbons from the foots oil and wax hydrocarbons. The subsequent sweating operation is likewise a fractionation for the same reason, accomplishing the separation of the wax hydrocarbons from the foots oil hydrocarbons. The foots oil is thus a twice fractionated product obtained by processes diiferent from those applied to any other petroleum fraction. We believe that the special properties of foots oil are due in part to these peculiar fractionations whereby it is obtained. No other product of petroleum has been subjected to this particular. combination of processes; therefore no other product has its particular properties. It is possible that these fractionations serve to segregate in the foots oil some special group of hydrocarbons which have a structural peculiarity responsible for the extraordinary behavior of the foots oil and distinguishing it from lubricating oil and wax hydrocarbons. The branched chain saturated hydrocarbons of high molecular weight, especially those with many branches and with long chain branches, are only very incompletely known; and their properties may well be the basis of the character of the foots oil on which we base our invention.

Broadly, our invention relates tothe reaction product of halogenated foots oil with a sulfur bearing material, as a new composition of matter or as an addition agent for use in lubricants. The chlorinated species has been referred to in particular because of the fact that it is usually cheapest and most easily manufactured. Our invention, however, does also contemplate the brominated, iodinated and fluorinated species, and of these the fluorinated species will be found particularly desirable on account of its stability.

We have found that a particularly useful derivative of halogenated foots oil may be prepared by treating halogenated foots oil which contains relatively reactive halogen with a sulfur-bearing reagent such as an inorganic hydrosulfide, or a sulfide, or a polysulfide, or a xanthate .or some similar sulfur-bearing material, so that the more reactive part of the halogen present in the halogenated foots oil will be replaced by the hydrosulflde, sulfide, polysulfide, xanthate, etc., radical.

the inorganic hydrosulfides, sulfides. polysulfldes,

xanthates. thiocarbonates, and other sulfur-bearing material as shown below. These may be in the form of metal salts or ammonium salts. The

metal salts that are particularly satisfactory are the sodium, potassium, lithium, calcium, barium. strontium, tin, and zinc salts. Illustrative examples of these sulfur-bearing materials are as follows:

A. Inorganic hydrosulfides: 1. Sodium hydrosulfide 2. Tin hydrosulflde 3. Lithium hydrosulfide Inorganic sulfides:

1. Hydrogen sulfide 2. Calcium sulfide 3. Zinc sulfide 4. Ammonium sulfide Inorganic polysulfides:

1. Phosphorus pentasulflde 2. Ammonium polysuliide 3. Potassium trisulflde 4. Phosphorus trisulfide Xanthates:

. Barium monochloroamylxanthate Lithium phenylxanthate Strontium benzyltinphenylxanthate Calcium cyclohexylxanthate Sodium phenyl a-bromolaurylxanthate Ammonium tolylxanthate Sulfurized tin linoleylxanthate Zinc furfuryl xanthate hiocarbonates: Sodium ethyltrithiocarbonate Ammonium p chloro benzylmonothiocarbonate Barium a-iodo amylphenyldithiocarbonate Strontium cyclohexyldithiocarbonate Sulfurized tin butenyltrithiocarbonat Sulfur-bearing material:

1. Elemental sulfur 2. Sulfur chloride The halogenated foots oil that has been reacted with a sulfur-bearing radical of the type listed above has markedly improved properties as an addition agent for lubricants. The chief characteristics that have'been noted to be imparted to the lubricant are anti-oxidant, corrosion inhibiting, and extreme pressure properties.

It is well known that in order to obtain lubricants that are pre-eminently satisfactory from the standpoint of oxidation in use it is necessary to refine the oil thoroughly and then to add an inhibitor of oxidation. The thorough refining may consist of more and heavier acid treatments or solvent treating so as to remove a considerable chaos part of the oil and leave only the most stablev portion. Such drastic refining is necessary in order to obtain stability with respect to sludge formation: but the oil is then subject to easy oxidation to form soluble acids and other corrosive materials. This can be prevented by the addition to the refined oil of small amounts of materials which either prevent the formation of these corrosive products or by some action render them inert. Furthermore, such well refined oils are susceptible to the formation during use of lacquer-like materials which tend to stick rings.

This results in blow-by and hence loss of power.

failure of lubrication, scratching, scoring, overheating, and' eventually replacement of parts. It is practically impossible to refine a lubricant in these conditions oxidation 'is slightly accelerated,

and' the products of oxidation react with the metals that they are in contact with (bearings, engine walls, crankcase, etc.) to form metal salts and soaps. These metal'salts or soaps, by catalytic action, greatly accelerate the further oxidation of the lubricant. These catalytic soaps and salts, however, on contact with our sulfur-bearing addends of this invention, react to form the insoluble metal sulfides or sulfide complexes which are inert. Thus the. catalyst having been renderedinert, the oxidation of the lubricant proceeds only at the normal rate, which in turn slows down or practically inhibits the corrosion of the metal parts of the lubricated equipment, as it is the oxidation products that have the corrosive effect.

bility in which the sulfur should be present. For

cutting or drawing oils, the sulfur should be in a very unstable or active form, while for certain other operating conditions the sulfur should be in a relatively more inactive or stable form. This is one major advantage in the products of this invention. Not only is the degree of the activity of the sulfur radical subject to control by selection of the sulfur-bearing material to be reacted with the halogenated foots oil, but it has been observed that the residual halogen in the reaction product has an unexpected and great effect upon the stability of the sulfur. The presence of the halogen greatly enhances the activity of the sulfur. Thus the addends of this invention are subject to a nicety of controlled activity entirely beyond the realm of any reasonable expectation.

The halogenated foots oil itself imparts improved extreme pressure characteristics to a lubricant; however the residual halogen in the prodnets of this invention imparts unexpectedly improved extreme pressure characteristics to a lubrigives a cant. The enhanced extreme pressure properties I are believed to be a result.of the activation of the halogen by the presence of the sulfur in the molecule. Whatever the explanation, the observed effect is within the contemplation of this invention.

Our addends are admirably adapted for use in lubricating oils of all types, including those designed for use in all types of operations, such as automobile crankcases, Diesel oils, greases, cutting and drawing oils, and any other oils of lubricating viscosity. They may be blended in mineral oil or any oil of lubricating viscosity, such as castor oil, cotton seed oil, lard oil, sperm oil, or shale oil. It may be desirable to include in one and the same blend based ona hydrocarbon oil, in addition to the addends here described, other addends forspecifio purposes. v

The addends contemplated in this invention and described above are effective in different con-p centrations. depending on mouse the lubricant 1. Treatment of tribromo foots oil of 20 C atoms with sodium hydrosulflde:

b. Na Br Br Br Br Br -H NaBr I Br ll3r Br Br S R- (I1 CH NaS-H -a Rik-(A41 NaBr or HBr Physical and chemical properties of.. a b I 4: Molecular weight 4 Under normal temperature is a Boiling pointunderreducedpressure 560 F. 6 Melting Point W l-60 F. Col brown or Solubility in water Solubility in organic solvent yes yes yes Range of boiling point approximate average boiling point given 2. Treatment of a penta chloro foots oil of 24 C atoms with an ammonium sulfide:

a. HH

emulsion H Cl 1 i All i Cl Cl Cl H\III III/H (31 S\ (I21 Boiling point at reduced pressure F. F.

Melting Point 0-10 F. 0-10 F. Range of boiling point approximate average boiling point given.

1 1 1i i i] 61 3. Treatment of dichloro foots oil of 24 C atoms H-N-H Oi Cl 01 H H H H Cl 01 \l I/ Physical and chemical to rties o! Molecularweight f? with lithium phenylxanthate: a. Cl

Ran e of boilin int r t point 81%. g 90 app oxima e average boiling 4. Treatment of dichloro foots oil of 24 C atoms with sodium ethyl trithiocarbonate:

o1 c1 R-c-rr m-s n-t-rr NaOl H-- -s n c=s Ba i-s Physical properties Molecular weight 508 Under normal conditions is a liquid Boiling point 475 F. Melting point 5-25? 1". Color darlr Solubility in water 0.08 In organic solvents good i Range oi boiling point approximate average boiling point given.

5. Treatment of dichloro foots oil of 24 C atoms with elemental sulfur:

Each of the above type reactions is well known to those skilled in the art; however for additional description of the preparation of the sulfur-bearing halogenated roots oil, the following remarks are made. It has been found that best results are obtainable when molal parts of each constituent are used as indicated by the equation of reaction. It has been found that the use of an excess of the sulfur-bearing constituents often hastens the reaction but that extreme methods of control must be used in order to maintain the desired residual halogen content. Usually it is necessary to heat the constituents in the reactor in a temperature range of between 200 degrees F. to 600 degrees F. for several hours with agitation. Organic solvents, such as xylene and benzene are used to hasten the reaction and may be separated from the reaction product by distillation after the separation of the inorganic salt such as metal or ammonium halides.

Other modes of applying the principle of the invention may be employed, change being made as regards the details described, provided the features stated in any of the following claims, or the equivalent of such be employed.

We, therefore, particularly point out and distinctly claim as our invention:

1. As a new composition of matter, the halogen and sulphur containing reaction product obtained by treating halogenated foots oil with an inorganic sulphur bearing material selected from the class consisting of inorganic hydrosulphides, inorganic sulphides, inorganic polysulphides, elemental sulphur, and sulphur chloride in a mole ratio of about 1:1 and at a temperature of from 200 F. to 600 F. with agitation.

2. As a new composition of matter, the halogen and sulphur containing reaction product obtained by treating chlorinated i'oots oil with an inorganic sulphur bearing material selected from the class consisting of inorganic hydrosulphides, in-.

organic sulphides, inorganic polysulphides, elemental sulphur, and sulphur chloride in a mole ratio of about 1:1 and at a temperature of from 200 F. to 600 F. with agitation.

3. A lubricating composition comprising a major proportion of an oil of lubricating viscosity and a minor proportion suflicient to impart extreme pressure and anti-oxidant characteristics to the oil of the halogen and sulphur bearing reaction product resulting from the treatment of halogenated foots oil with an inorganic sulphur bearing material selected from the class consisting of inorganic hydrosulphides, inorganic sulphides, inorganic polysulphides, elemental sulphur. and sulphur chloride in a mole ratio of about 1:1 and at a temperature of from 200 F. to 600 F. with agitation.

4. A lubricating composition comprising a major proportion of an oil of lubricating viscosity and a minor proportion suflicient to impart extreme pressure and anti-oxidant characteristics to the oil of the halogen and sulphur bearing reaction product resulting from the treatment of chlorinated foots oil with an inorganic sulphur bearing material selected fromthe class consisting of inorganic hydrosulphides, inorganic sulphides, inorganic polysulphides, elemental sulphur, and sulphur chloride in a mole ratio of about 1 1: 1 and at a temperature of from 200 F. to 600 F.

with agitation.

5. A lubricating composition comprising a major proportion of an oh of lubricating viscosity and a minor proportion sufficient to impart extreme pressure and anti-oxidant characteristics to the oil of the halogen and sulphur bearing reaction product of a chlorinated foots oil containing on the order of about 10% to 60% of chlorine with a sulphur bearing material selected from the class of inorganic hydrosulphides, inorganic sulphides, inorganic polysulphides, elemental sulphur, and sulphur chloride in a mole ratio of about 1:1 and at a temperature of from 200 F. to 600 F. with agitation.

6. A lubricating composition comprising a major proportion of an oil of lubricating viscosity and .001-10 per cent by weight of the final lubricating composition of the halogen and sulphur bearing reaction product of a chlorinated foots oil containing on the order of about'10% to 60% of chlorine with a sulphur bearing material selected from the class consisting of inorganic hydrosulphides, inorganic sulphides, inorganic polysulphides, elemental sulphur, and sulphur chlo- 4 hearing reaction product resulting from the treatment of chlorinated foots oil with an inorganic sulphur bearing material selected from the class consisting of inorganic hydrosulphides, inorganic sulphides, inorganic polysulphides, elemental sulphur, and sulphur chloride in a mole ratio of about 1:1 and at a temperature of from 200 F. to 600" F. with agitation.

8. A lubricating composition comprising a major proportion of an oil of lubricating viscosity and a minor proportion suflicient to impart exride in a mole ratio of 1:1 and at a temperature of from 200 F. to 600 F. with agitation.

7. A lubricating composition comprising a major proportion of an oil of lubricating viscosity and .001-10 per cent by weight of the final lubricating composition of the chlorine and sulphur treme pressure and anti-oxidant characteristics to the oil of the chlorine and sulphur bearing reaction product resulting from the treatment of chlorinated foots oil with a phosphorus polysulphide in a mole ratio of about 1:1 and at a temperature of from 200 F. to 600 F. with agitation. 9. A lubricating composition comprising a major proportion of an oil of lubricating viscosity and a minor proportion sufficient to impart extreme pressure and anti-oxidant characteristics to the oil of the chlorine and sulphur bearing reaction product resulting from the treatment of chlorine bearing foots oil with elemental sulphur in a mole ratio of about 1:1 and at a temperature of from 200 F. to 600 F. with agitation. I

10. A lubricating composition comprising a major proportion of an oil of lubricating viscosity and a minor proportion sufficient to impart extreme pressure and anti-oxidant characteristics to the oil and sulphur bearing reaction product resulting from the treatment of chlorinated foots oil with sulphur chloride in a mole ratio of about 1:1 and at a temperature of from 200 F. to 600 F.

with agitation.

. BERT H. LINCOLN.

GORDON D. BYRKIT.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Zimmer Feb. 16, 1943 

